Photochromic compound and composition containing the same

ABSTRACT

WHEREIN R1 REPRESENTS-(CH2)NCOOH,-(CH2ENCN OR -(CH2)NCOOR (WHEREIN R IS AN ALKYL GROUP HAVING 1 TO 5 CARBON ATOMS; N IS 1 TO 4); R2 AND R3 REPRESENT AN ALKYL GROUP HAVING 1 TO 5 CARBON ATOMS OR A PHENYL GROUP; AND R4 REPRESENTS A HYDROGEN ATOM, AN ALKYL GROUP HAVING 1 TO 5 CARBON ATOMS; A HALOGEN ATOM, A NITRO GROUP, A CYANO GROUP, OR AN ALKOXYL GROUP HAVING 1 TO 5 CARBON ATOMS OR A CARBOXYL GROUP, AND SAID CARBOXYL GROUP MAY BE SUBSTITUTED WITH AN ALKYL GROUP HAVING 1 TO 5 CARBON ATOMS.   OXAZINE)   1-R1,3-R2,3-R3,R4-SPIRO(INDOLINE-2,3&#39;&#39;-NAPHTH(2,1-B)-1,4-   PHOTOCHROMIC COMPOSITIONS CONTAINING, AND PHOTOCHROMIC COMPOUNDS PER SE, REPRESENTED BY THE FORMULA:

Feb. 9, 1971 v l T 0 0 ETAL 3,562,172

PHOTOCHROMIC COMPOUND AND COMPOSITION CONTAINING THE SAME Filed 001..28, 1969 DENSRTY (DI WAVE LENGTH INVENTORS HiSATAKE 0N0 I CHIAKI OSADA sjl w im M ATTORNEYS United States Patent Ofice 3,562,172 Patented Feb.9, 1971 U.S. Cl. 252-300 10 Claims ABSTRACT OF THE DISCLOSUREPhotochromic compositions containing, and photochromic compounds per se,represented by the formula:

wherein R represents (CH ),,COOH, (CH ),,CN or -(CH ),,COOR (wherein Ris an alkyl group having 1 to carbon atoms; n is 1 to 4); R and Rrepresent an alkyl group having 1 to 5 carbon atoms or a phenyl group;and R represents a hydrogen atom, an alkyl group having 1 to 5 carbonatoms; a halogen atom, a nitro group, a cyano group, or an alkoxyl grouphaving 1 to 5 carbon atoms or a carboxyl group, and said carboxyl groupmay be substituted with an alkyl group having 1 to 5 carbon atoms.

BACKGROUND OF THE INVENTION Field of the invention This inventionrelates to photochromic materials. The present invention relates to aphotochromic compound represented by the formula wherein R represents-(CH ),,COOH, -(CH ),,CN or -(CH ),,COOR (wherein R is an alkyl grouphaving 1 to 5 carbon atoms; n is 1 to 4); R and R represent an alkylgroup having 1 to 5 carbon atoms or a phenyl group; and R represents ahydrogen atom, an alkyl group having 1 to 5 carbon atoms; a halogenatom, a nitro group, a cyano group, or an alkoxyl group having 1 to 5carbon atoms or a carboxyl group, and said carboxyl group may besubstituted with an alkyl group having 1 to 5 carbon atoms.

Description of the prior art We previously discovered the photochromiccompound represented by the above formula, in which R is an alkyl group,as disclosed in Japanese patent application No. 55,662/67. Thephotochromic action of the compound was remarkable at about 10 C.

SUMMARY OF THE INVENTION Photochromic composition containing, andphotochromic compounds per se, represented by the formula:

wherein R represents -(CH ),,COOH, (CH CN or (CH ),,COOR (wherein R isan alkyl group having 1 to 5 carbon atoms; 11 is 1 to 4); R and Rrepresent an alkyl group having 1 to 5 carbon atoms or a phenyl group;and R represents a hydrogen atom, an alkyl group having 1 to 5 carbonatoms, a halogen atom, a nitro group, a cyano group or an alkoxyl grouphaving 1 to 5 carbon atoms or a carboxyl group, and said carboxyl groupmay be substituted with an alkyl group having 1 to 5 carbon atoms.

An object of the present invention is to obviate the disadvantagesdiscussed above and to provide a novel compound having an oxazine ringto replace the conventional compounds having a pyrane ring.

Another object of the present invention is to provide a photochromiccompound which is not influenced by the polar nature of the solvent, andwhich illustrates photochromic action at normal temperatures.

BRIEF DESCRIPTION OF THE DRAWINGS The drawing is a plot of densityversus wavelength for a compound of the invention before and afterirradiation with ultraviolet rays.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present inventionrelates to a photochromic compound represented by the formula wherein Rrepresents -(CH ),,COOH, (CH CN or (CH ),,COOR (wherein R is an alkylgroup having 1 to 5 carbon atoms; is is l to 4); R and R represent analkyl group having 1 to 5 carbon atoms or a phenyl group; and Rrepresents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms; ahalogen atom, a nitro group, a cyano group, or an alkoxyl group having 1to 5 carbon atoms or a carboxyl group, and said carboxyl group may besubstituted with an alkyl group having 1 to 5 carbon atoms.

The compound represented by the above formula is dissolved in a solventsuch as benzene, toluene, carbon disulfide, ethyl acetate, methyl ethylketone, acetone, ethyl alcohol, methyl alcohol, acetonitrile,tetrahydrofurane, dioxane, methyl cellusolve morpholine, ethyleneglycol, dimethyl formamide, dimethyl sulfoxide, etc. (at normaltemperature) to yield the photochromic composition in a colorlas state.When it is irradiated with ultraviolet rays, the photochromiccomposition turns blue. Further, the compound of the present inventioncan be dissolved in a solution such as polyvinylacetate-acetonesolution, nitrocellulose-acetonitrile solution, polyvinylchloride-methylethyl ketone solution, polymethylacrylate acetone solution, celluloseacetate-dimethyl formaldehyde solution,polyvinylpyrrolidone-acetonitrile solution, polystyrol-benzene solution,ethyl cellulose-methylene chloride solution, etc., to obtain thephotochromic composition in a colorless state, regardless of the kindsof solvents and/ or resins.

The composition can be coated on a support such as baryta paper,cellulose acetate, polyethylene terephthalate, etc., and then dried, andwill still turn blue when irradiated with ultraviolet rays and, ifallowed to stand in the dark without exposure to ultraviolet rays, willchange to colorless again.

The compound represented by the above formula is obtained by refluxing aquaternized indolenine derivative, u-nitroso-fi-naphthol andtriethylamine in an approximate equimolar ratio in ethyl alcohol whilepassingnitro gen gas through the system, followed by cooling, filteringand recrystallizing from an appropriate solvent.

The photochromic compositions of the present inven tion are employed asphotochromic materials for photography and printing, which are obtainedby coating the above composition on a high molecular weight film, barytapaper, etc., photochromic materials for furniture usage such ascurtains, glass, etc., and photochromic materials for use in filters.

The figure is a graph showing the change in the visible absorptionspectrum of film, before and after irradiation with ultraviolet rays,which is coated with the photochromic composition of this invention,then dried.

EXAMPLE 1 6.2. g. of l-B-carboxyethyl-2,3,3-trimethyl-indolenium bromideand 3.5 g. of u-nitroso-B-naphthol were dissolved in 50 cc. ofdehydrated ethanol and, after adding 2 g. of triethylamine thereto, wererefluxed in a nitrogen atmosphere for two hours. After the reaction,excess ethanol was distilled out and the mixture was cooled to produce acrystal. A small amount of ethanol was added thereto and filtered. Thecrude crystal thus obtained was recrystallized from ethanol using activecarbon to provide 0.7 g. of the yellow crystal of 1-3-carboxyethyl-3,3-dimethyl spiro[indolino-2,3'-naphtho[2.1-b](1.4)oxazine] having a melting point of 186 to 187 C. The ethanolsolution of this compound was colorless under the light of a room lamp,but, when irradiated with ultraviolet rays, immediately colored blue,and turned back to colorless when allowed to stand in a dark place.

EXAMPLE 2 3.3 g. of l-/3-carb0xyethyl-2,3,3,S-tetramethyl-indoleniumbromide and a-nitroso-p-naphthol were reacted in the same manner as inExample 1 to obtain 1.2 g. of the yellow crystals ofl-B-carboxyethyl-3,3,5-trimethyl spiro [indolino 2,3 naphtho[2.1-b](1.4) oxazine] having a melting point of 188 to 190 C. A benzenesolution of this compound was colorless, but, when irradiated withultraviolet rays, colored greenish blue and, on being al lowed to standin the dark, turned back to colorless. A baryta paper which 'was coatedwith a solution of this compound dissolved in ethyl acetateester-polyvinyl acetate and dried was colorless in the ordinary state,but, when irradiated with ultraviolet rays, immediately colored blue.Upon discontinuing irradiation with ultraviolet rays, this materialturned colorless. The absorption curve for this material is shown inFIG. 1. Curve 1 is before irradiation, and curve 2 is after irradiation.

EXAMPLE 3 6.8 g. of 1-carboxyethyl-2,3,3-trimethyl-5-methoxyindoleniumbromide and 3.5 g. of a-nitroso-B-naphthol were reacted in the samemanner as in Example 1 to obtain 2.1 g. of the light yellow crystal of1-carboxyethyl-3,3-

4 dimethyl-S-methoxy spiro[indolino 2,3'-naphtho[2.l-b]

(1.4)oxane] having a melting point of 165 to 167 C.

The properties thereof were the same as the compound of Example 2.

EXAMPLE 4 6.8 g. of 1-'y-cyanopropyl-2,3,3-trimethyl-5-chlorindoleniumbromide and 3.5 g. of oc-nitroso-B-naphthol were reacted in the samemanner as in Example 1 to obtain 2.1 g. of the light yellow crystals of1- -cyanopropyl-3,3- dimethyl 5 chlor-spiro[indolino-2,3'-naphtho[2.1 b](1.4)oxazine] which melts at 158 to 160 C. A polyethylene terephthalatefilm coated with a solution of this compound dissolved inbenzene-polystyrol and dried was colorless and transparent, but, whenirradiated with ultraviolet rays, immediately colored blue and, onallowing to stand in the dark turned back to colorless.

We claim:

1. A photochromic compound represented by the general formula,

R2 Ra wherein R represents -(CH COOH, (CH CN, or -(CH COOR; R is analkyl group having 1 to 5 carbon atoms; n is 1 to 4; R and R representan alkyl group having 1 to 5 carbon atoms or a phenyl group; Rrepresents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms; ahalogen atom, a nitro group, a cyano group, an alkoxyl group having 1 to5 carbon atoms, a carboxyl group or a carboxyl group being substitutedwith an alkyl group having 1 to 5 carbon atoms.

2. The photochromic compound as claimed in claim 1 wherein said compoundrepresented by the general formula is 1-3-carboxyethyl-3,3-dimethyl-spiro [indolino-2,3 naphtho[2.1-b] (1.4)oxazine] 3. The photochromic compound as claimed in claim 1 wherein saidcompound represented by the general formula isl-fi-carboxyethyl-3,3,S-trimethyl-spiro[indolino-2, 3-naphtho[2.1-b](1.4)oxazine].

4. The photochromic compound as claimed in claim 1 wherein said compoundrepresented by the general formula is 1carboxyethyl-3,3-dimethyl-5-methoxy-spiro [indolino-2,3'-naphtho [2.l-b] (1.4)oxazine].

5. The photochromic compound as claimed in claim 1 wherein said compoundrepresented by the general formula is l-y-cyanopropyl 3,3dimethyl-S-chloro-spiro [indolino-2,3 '-naphthol[2.1-b] (1.4)oxazine].

6. A photochromic composition comprising a photochromic compoundrepresented by the general formula,

wherein R represents (CH ),,COOH, (CH ),,CN or (CH COOR; R is an alkylgroup having 1 to 5 carbon atoms; and n is 1 to 4; R and R eachrepresents an alkyl group having 1 to 5 carbon atoms or a phenyl group;and R represents a hydrogen atom, an alkyl group having 1 to 5 carbonatoms, a halogen atom, a nitro group, a cyano group, an alkoxy grouphaving 1 to 5 carbon atoms, a carboxyl group or a carboxy groupsubstituted with an alkyl group having 1 to 5 carbon atoms, and asolvent.

7. The photochromic composition as claimed in claim 6 wherein saidsolvent is benzene, toluene, carbon disulfide, chloroform, ethylacetate, methyl ethyl ketone,

wherein R represents -(CH COOH, (CH CN or (CH COOR; wherein R is analkyl group having 1 to 5 carbon atoms; n is 1 to 4; R and R eachrepresents an alkyl group having 1 to 5 carbon atoms; and R represents ahydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogenatom, a nitro group, a cyano 20 group, an alkoxyl group, a carboxylgroup, or a carboxy group substituted with an alkyl group having 1 to 5carbon atoms, a binder and a solvent.

9. The photochromic composition as claimed in claim 8 wherein saidbinder is polyvinyl acetate, nitrocellulose, polyvinyl chloride,polymethylmethacrylate, cellulose acetate, polyvinyl pyrrolidone,polystyrene or ethyl cellulose.

10. The photochromic composition as claimed in claim 9 wherein saidsolvent is acetone, acetonitrile, methyl ethyl ketone, dimethylformamide, acetonitrile, benzene or methylene chloride.

References Cited UNITED STATES PATENTS 3,395,145 7/1968 Hansen et al260244 GEORGE F. LESMES, Primary Examiner J. P. BRAMMER, AssistantExaminer US. Cl. X.R. 260244

